Capillary gas chromatography-mass spectrometry of resin acids in tall oil rosin

The resin acid composition of Finnish tall oil rosin was investigated by gas chromatography and mass spectrometry employing open tubular capillary columns. On a column coated with 1,4-butanediol succinate, 16 resin acids found in tall oil rosin samples were well resolved, and mass spectra could be recorded. All resin acids were confirmed to be of the pimaric and abietic types by gas chromatographymass spectrometry. Eight of the acids were not detected in the corresponding crude tall oils and evidently had been formed during the technical distillation process. The presence of 8,15-pimaradien-18-oic and 8,15-isopimaradien-18-oic acids in the rosin, but not in the crude tall oil, indicates that the pimaric type acids also undergo extensive isomerization during tall oil distillation. Additionally, three dihydroabietic acids and two acids with identical mass spectra, tentatively stereoisomers of 7,9(11)-abietadien-18-oic acid, were formed during the distillation process.     

Improved gas chromatographic analysis of fatty and resin acid mixtures with special reference to tall oil

A gas liquid chromatography system for the analysis of complex mixtures of fatty and resin acids has been developed. On 30–40 m long, 0.3 mm ID glass capillary columns coated with 1,4-butanediol succinate (BDS) and attaining over 90,000 effective theoretical plates, all main fatty and resin acids in wood extractives and various tall oil products can be separated and quantitatively determined without need of any prefractionation of the acids. Also the levopimaric acid is well separated. Retention values, including their temperature dependence, on columns coated with BDS or SE-30 are given for 49 significant fatty and resin acids. Applications on wood extractives, sulfate soaps, and crude and distilled tall oil are presented and discussed.     

Gas chromatographic separation of diterpene acids on glass capillary columns of different polarity

Mixtures of resin acids from tall oil distillation products and from naturally occurring rosins (colophony) were separated on WCOT glass capillary columns coated with SE 30, FFAP, DEGS and BDS, and the resin acids were identified by gas chromatography-mass spectrometry (GC-MS). In contrast to previous investigations, the identified diterpene acids are characterized by Kovats index values. These retention values are correlated with the different polarity of the stationary phase. The advantages of columns coated with FFAP for the separation of crude and distilled tall oil and fatty acid samples are discussed. Dedicated to Prof. Dr. Erich Ziegler at his 70th birthday     

The behavior of resin acids during tall oil distillation

The behavior of resin acids during tall oil distillation was studied by analyzing samples from six industrial-scale processes. The same artifact resin acids were formed in all processes. However, the proportion of artifact resin acids in tall oil rosins varied from 8.3 to 18.3% of the resin acids. The lowest values were found for two processes utilizing thin-film evaporators. The yield of resin acids in the tall oil rosin fraction varied from 62 to 80% of the resin acids in the crude tall oil feeds. Dehydroabietic acid was formed in all processes, the amount in rosin being 14-44% more than in the crude tall oil feed. Of the abietic acid, only 45-82% was recovered in the tall oil rosin fraction. The distribution of various resin acids and their reaction products during distillation was determined. Major resin acid impurities in tall oil fatty acids were 8,15-pimaradien-18-oic acid and 8,15-isoprimaradien-18-oic acid, both formed chiefly during distillation, and two secodehydroabietic acid isomers common in crude tall oils. The reactions of resin acids leading to new isomers or non-acidic products are discussed. Some results of this work were presented at the 173rd American Chemical Society Meeting, New Orleans, March 1977.     

Destillationsprobleme der Tallölaufbereitung

Problems of Distillation in the Processing of Tall Oil Large scale distillation of tall oil for the separation of the major components, fatty acids and rosin acids, involves difficulties owing to the presence of numerous other components, which, under the conditions of distillation, react with the active groups of the acids and the double bonds. The present communication shows the conditions which minimize such undesirable side reactions and additional thermal and oxidative decompositions, that reduce the yield of fatty acids and rosin acids. According to process, developed by the author, a countercurrent degasing and dewatering treatment with stripping steam is carried out before the separation of pitch, in order to remove rapidly at low temperatures the volatile substances, which negatively affect the odour, colour and colour stability. A vacuum of 100 torr enables the condensation of fairly large amounts of the stripping steam used by means of cooling water. Thus, the vacuum system is not affected. The distillative separation of pitch is carried out in two stages. The temperature of tall oil reaches a maximum of 230°C for the recovery of 90% of the distillate. In the second stage of film evaporation, the temperature of the product reaches 255°C for a short period. In the final distillation of the mixture of fatty acids and rosin acids, free of pitch, ACV-trickle columns and specially constructed falling film evaporators are used, which ensure that the temperature of the still does not exceed 260°C and the excess temperature of the heating medium is not more than 20°C. In case the temperature of the product exceeds 250°C in the falling film evaporator, addition of a few percent of stripping steam at their heads prevents the undesirable formation of anhydride.     

Distillability of extracted mixed-birch tall oil

Chemical and physical properties of tall oil made in the CSR process and distillation results of three different types of distillation plants are presented. Chemically extracted, mixed-birch, tall oil differs remarkably from the normal Scandinavian crude tall oil. The extracted oil deviates from the normal, unextracted, mixed-birch tall oil with respect to the smaller unsaponifiable amount and the fatty acid esters. The amount of resin acid is small in extracted mixed-birch tall oil. The quantity of fatty acids, especially that of saturated fatty acids, is large. Distillation of extracted mixed-birch tall oil is most successful in a distillation plant where thin film evaporators are used.     

Diterpene resin acids: Major active principles in tall oil against Variegated cutworm,Peridroma saucia (Lepidoptera: Noctuidae)

Tall oil, a by-product of the kraft process for pulping softwood, has been shown to have insecticidal properties. In the present study, the active principles in tall oil against the variegated cutworm,Peridroma saucia Hübner, were investigated. GC-MS analysis showed that abietic, dehydroabietic, and isopimaric acids were major resin acid components of crude tall oil and depitched tall oil. When crude tall oil samples of differing resin acid composition were incorporated into artificial diet at a concentration of 2.0% fresh weight, they suppressed larval growth by 45–60% compared to controls. This suppression was significantly (P0.05) correlated with the equivalent contents of abietic, dehydroabietic, isopimaric, and total resin acids. These results were also evident from a diet choice test, showing that the second-instar larvae obviously selected diets with low levels of resin acids when different diets were randomly arranged in a Petri dish. Bioassays with pure resin acids (abietic, dehydroabietic, and isopimaric acids) demonstrated that all individual chemicals have similar bioactivity against this insect. Comparison of the bioactivities of depitched tall oil and an equivalent mixture of pure resin acids in thePeridroma chronic growth bioassay indicated that pure resin acids and depitched tall oil share a common mode of action to this insect. This study confirms that resin acids are major active principles in tall oil against the variegated cutworm, but other chemicals likely also contribute to the bioactivity of tall oil.     

Utilization of tall oil to enhance natural fibers for composite applications and production of a bioplastic

Tall oil is one of the side products from the kraft pulping process of lignocellulosic material. The most abundant acid found in this crude viscous material is abietic acid. Strangely, in the past, the utilization of tall oil has been limited to incineration for cogeneration of power. In this study, tall oil rosin acids (TORAs) were used in two different applications. First, it was used to enhance the hydrophobicity and thermal properties of hemp fibers. Second, TORAs were used to supplement epoxy for the production of a polymeric material. The reaction conditions from a model study were mimicked using a crude tall oil rosin acid mixture to enhance hemp fibers. Treated hemp fibers were characterized with increased surface hydrophobicity and improved thermal properties. Also, IR and X‐ray photoelectron spectroscopy confirmed successful chemical modification and grafting of carbon rich moieties onto the surface of the fibers, respectively. Furthermore, TORAs were used to supplement epoxy resin and produced plastics with comparable properties to pure epoxy based plastics. Specifically, 25% (w/w) replacement exhibited little difference in thermal stability and curing when compared to virgin epoxy plastics. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44327.     

Tall oil fatty acid marketing

Once considered a low cost by-product of crude tall oil fractionation, tall oil fatty acids are now being used for their own distinctive and specific properties in special applications. Consumption of tall oil fatty acids in protective coatings, soaps, and ore flotation has declined in recent years, however, usage in chemical intermediates has increased significantly in the past 10 years. These intermediates are dimer acids, oleic and linoleic acids, epoxidized esters, amidoamines, and diacids. Static tall oil production during the mid 1970s caused by changes in paper mill operations (i.e., continuous digestion, waste recycling, increased usage of chips and hard wood) has increased the demand for higher priced oleic acid and other unsaturated fatty acids.     

Tall oil fatty acids

About 1949, with the advent of effective fractional distillation, the tall oil industry came of age, and tall oil fatty acids (TOFA), generally any product containing 90% or more fatty acids and 10% or less of rosin, have grown in annual volume ever since, until they amount to 398.8 million pounds annual production in the U.S. in 1978. Crude tall oil is a byproduct of the Kraft process for producing wood pulp from pine wood. Crude tall oil is about 50% fatty acids and 40% rosin acids, the remainder unsaps and residues; actually, a national average recovery of about 1–2% of tall oil is obtained from wood. On a pulp basis, each ton of pulp affords 140–220 pounds black liquor soaps, which yields 70–110 pounds crude tall oil, yielding 30–50 pounds of TOFA. Separative and upgrading technology involves: (a) recovery of the tall oil; (b) acid refining; (c) fractionation of tall oil; and occasionally (d) conversion to derivatives. TOFA of good quality and color of Gardner 2 corresponds to above 97% fatty acids with the composition of 1.6% palmitic & stearic acid, 49.3% oleic acid, 45.1% linoleic acid, 1.1% miscellaneous acids, 1.2% rosin acids, and 1.7% unsaponifiables.     

Production methods for the manufacture of crude tall oil and its subsequent processing

Summary The source of crude tall oil and methods to produce the oil have been described. These include acidulation of sulfate pulp, black liquor skimmings, and gravity settling as well as centrifugal means of separation to reduce the lignin content of the product. Subsequent processing of the crude tall oil into fractionated fatty acids and rosin has been outlined with suggestions for consideration in all stages of the distillation section of the plant.     

Solvent extraction of fatty acids from natural oils with liquid water at elevated temperatures and pressures

The use of liquid water at elevated temperatures and pressures as an extractive solvent for separating mixtures of compounds which occur in natural oils has been studied. A southern pine tall oil and a distillate from the deodorization of soybean oil were extracted with liquid water at temperatures from 298 to 312°C and pressures between 103 and 121 bar. Results indicate that water can be used to extract fatty and resin acids from crude tall oil to obtain a product with a high acid content that produces less pitch during distillation. The process can also be used to extract fatty acids from vegetable oil deodorizer distillate.     

Schonende destillative Zerlegung der Fettsäuren von Kokos-, Palmkern- und Palmöl unter Berücksichtigung der Wirtschaftlichkeit und des Umweltschutzes

Distillative Fractionation of Fatty Acids of Coconut, Palm Kernel and Palm Oil under Mild Conditions with Consideration of Economy and Environmental Safety . Present study deals with the question as to how pure and marketable products can be produced from coconut, palm kernel and palm oil fatty acids at a minimum expenditure on plant and operation. Factors concerning environmental safety are considered besides the influence of the number of columns and plates as well as that of the reflux ratio. The most suitable combination for processing such crude acids, from economic view-point, is a two-column system, preceded by a film degassifying unit for simultaneous degassing, dehydration and deodorization, and followed by a falling film evaporator with forced circulation for the separation of tar.     

Biodiesel production from tall oil with synthesized Mn and Ni based additives: Effects of the additives on fuel consumption and emissions

In this study, biodiesel fuel and fuel additives were produced from crude tall oil that is a by-product in the pulp manufacturing by craft or sulphate pulping process. Fatty acids and resinic acids were obtained from crude tall oil by distillation method. Tall oil methyl ester (biodiesel) was produced from fatty acids. Resinic acids were reacted with NiO and MnO₂ stoichiometrically for production of metallic fuel additives. Each metallic fuel additive was added at the rate of 8 μmol/l and 12 μmol/l to make mixtures of 60% tall oil methyl ester/40% diesel fuel (TE60) for preparing test fuels. Metallic fuel additives improved properties of biodiesel fuels, such as pour point and viscosity values. Biodiesel fuels were tested in an unmodified direct injection diesel engine at full load condition. Specific fuel consumption of biodiesel fuels increased by 6.00%, however, in comparison with TE60, it showed trend of decreasing with adding of additives. Exhaust emission profile of biodiesel fuels improved. CO emissions and smoke opacity decreased up to 64.28% and 30.91% respectively. Low NO_x emission was also observed in general for the biodiesel fuels.     

Zu den Veränderungen von Rapsöl und Leinöl während der Verarbeitung

Changes of rapeseed and linseed oil during processing During processing of crude oil in a large oil mill, three samples each of rapeseed and linseed were investigated at each processing stage, i.e. press oil, solvent-extracted oil, mixed oil, and degummed/caustic refined oil. In the case of rapeseed also bleached and desodorized oils (230°C; 3.0 mbar for 2 h) were investigated. Rapeseed and linseed oil showing the typical major fatty acids contained less than 1% trans-isomeric fatty acids (trans fatty acids = TFA). Linseed oil had a similar TFA-concentration as rapeseed oil, and the concentrations did not change during the processing stages up to degummed/caustic refined oil, and were also unchanged in the bleached rapeseed oil. Desodorization of rapeseed oil, however, trebled the TFA concentration to 0.58%. The detected tocopherol patterns were typical of rapeseed and linseed oils. There was no difference between mixed oil and degummed/caustic refined oil in the total concentration of tocopherols. Neither had bleaching any effect. Rapeseed oil desodorization diminished total tocopherol concentration by 12% from 740 mg/kg to 650 mg/kg. Due to degumming/caustic refining the phosphorus concentration of both oils decreased to less than a tenth compared to mixed oil. Other elements determined in degummed/caustic refined rapeseed oil were not detectable (manganese < 0.02 mg/kg, iron < 0.4 mg/kg, copper < 0.02 mg/kg, lead < 10 μg/kg) or only as traces zink 0.1 mg/kg, cadmium 2 μg/kg). In linseed oil, which initially showed a higher trace compounds concentration, a significant decrease was found by degumming/caustic refining. Iron could not be detected. There were traces of zinc, manganese, copper, lead, and cadmium. There was no difference between the acid values of rapeseed and linseed crude oil. Acid value decreased drastically already during the degumming/caustic refining stage. The crude linseed oils had a higher peroxide value, anisidine value and diene value than the corresponding crude rapeseed oils. With peroxide values of ≤ 0.1 mEq O₂/kg found in almost all investigated rapeseed oils, no effect of refining could be detected. The anisidine value showed an increase after bleaching. Desodorization trebled the diene value.     

Methoden zur Verbesserung der Destillation von Tallöl

New Method for the Improvement of Tall Oil Distillation Experimental results are reported on the distillation of tall oil in a pilot plant as well as in an industrial unit. The process involves the use of thin-film evaporators that enable short time of contact. Thus the yield of pitch is decreased. Undesirable side reactions, such as esterification, decarboxylation and polymerization are reduced. The typical characteristics of the fractions obtained have been investigated and correlated with the operational data. It is shown that since the pretreatments of the product such as heating, dehydration and separation of pitch are carried out under very mild conditions, the subsequent fractionation of resin acids and fatty acids into fractions having low content of unsaponifiables can easily be achieved.     

Industrial Waste Materials as a Source of Sterols

The content of sterols and their derivatives have been examined in the following industrial waste materials: oily bleaching earth, volatiles from deodorization of oils, residue after distillation of tall oil, residue after distillation of crude animal and plant fatty acids. Amount of sterols directly occurring in such raw materials as low erucic and high erucic rapeseed oil and tall oil has also been stated. The quality constitution of sterols contained in those raw materials has been estimated. The profitability of getting sterols from those sources for the purposes of the cosmetic and pharmaceutical industries have been considered.     

Spectrophotometric analysis of tall oil rosin acids

Summary About half of the rosin acids in whole and distilled tall oil consist of abietic and neoabietic acids, as distinguished from hydroabietic acids, dehydroabietic acid, and the pimaric acids. In this respect the tall oil rosin acids are similar to those from gum or wood rosin. This was established by spectrophotometric analysis of the rosin acids from whole tall oil, double distilled tall oil, rosin acids crystallized from tall oil, and rosin acids separated from tall oil by fractional distillation. The rosin acids crystallized from tall oil contained the highest percentage of abietic acid, but the sum of abietic and neoabietic acids was only slightly higher. The rosin acids from acid refined tall oil contained appreciably less abietic and neoabietic acid than the others. Before spectrophotometric analysis the rosin acids were isolated from the tall oils in about 95% yield by cyclohexylamine precipitation.     

Probleme der großtechnischen destillativen Aufarbeitung von Rapsölfettsäuren

Problems in the Distillation of Rapeseed Fatty Acids on a Technical Scale The present study concerns large scale recovery of pure fatty acids from unhydrogenated or hydrogenated crude fatty acids of rapeseed. The number of theoretical plates and reflux ratios that are required for the fractionation of the starting materials having different compositions are given with consideration to the thermal behaviour of the components and the required temperature and pressure. ACV-type stretched metallic packings and falling film evaporators with forced circulation and vapour by-pass have been found suitable for large scale fractionation. Construction, working principle and efficiency of one such ACV plant consisting of a degassing unit, two trickle columns and a final evaporator are discussed.     

Carotinanalysen in rohem Palmöl

Analysis of Carotenes in Crude Palm Oil Structure and properties of natural carotenes as well as their behaviour especially towards adsorbents are discussed. Literature on the occurrence of carotenes in palm oil is reviewed and a short history of the development of analytical methods for the separation of carotenes is presented. A tentative method of the DGF for the analysis of minor components is reported, which enables quantitative determination of the total carotenes as well as α and β-carotenes, separately in fats and oils. Usefulness of this method is shown in the analysis of 10 samples of crude palm oil from various sources. Determination of free fatty acids and peroxides round up the analytical picture of palm oil samples.